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CN113828327A - Catalyst, preparation method and application thereof, and method for preparing olefin through alkane dehydrogenation - Google Patents

Catalyst, preparation method and application thereof, and method for preparing olefin through alkane dehydrogenation Download PDF

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CN113828327A
CN113828327A CN202010591650.3A CN202010591650A CN113828327A CN 113828327 A CN113828327 A CN 113828327A CN 202010591650 A CN202010591650 A CN 202010591650A CN 113828327 A CN113828327 A CN 113828327A
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catalyst
weight
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CN113828327B (en
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姜冬宇
吴文海
樊志贵
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/322—Catalytic processes with metal oxides or metal sulfides
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a catalyst which is a composite catalyst and comprises the following components: a) 0.1-5 parts by weight of Pt element; b)0.1 to 5 parts by weight of Sn element; c)0.1 to 2 parts by weight of an alkaline earth metal element; d) 0.1-2 parts by weight of rare earth elements; e) 90-99 parts by weight of a composite oxide A-B-Al-O carrier, wherein A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements. The initial temperature Ts at which the Sn component begins to be reduced to Sn is 650-700 ℃ measured by a hydrogen programmed heating method. The catalyst of the invention can better solve the problem of lower stability of the dehydrogenation catalyst prepared by the prior art, and can be particularly used for the industrial production of propylene by propane dehydrogenation.

Description

Catalyst, preparation method and application thereof, and method for preparing olefin through alkane dehydrogenation
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, and a method for preparing olefin by alkane dehydrogenation by using the catalyst.
Background
Propylene is a very important organic chemical raw material, which together with ethylene and isobutylene is considered as the basis of modern petrochemical industry, the most important purpose being for the production of polypropylene and secondly for the production of acrylonitrile. The traditional method for obtaining propylene adopts ethylene coproduction and naphtha and light diesel cracking process, but in recent years, the demand of human beings on worldwide petrochemical raw materials and petrochemical products is continuously increased, the demand of propylene and isobutene serving as petrochemical basic raw materials is continuously increased, the traditional conventional method cannot meet the increased demand, and thus scientists are consistently dedicated to developing a new route for obtaining the target propylene. Among them, a method of producing propylene by a direct dehydrogenation process using propane as a raw material in petrochemical byproducts, natural gas, or the like has been attracting attention in recent years, and is particularly favored in regions rich in propane resources.
The technology for preparing propylene by propane dehydrogenation has been known for about 30 years, and the industrialized or successfully developed propane catalytic dehydrogenation technology comprises an Oleflex process of UOP company, a Catofin process of CB & I Lummus company, a fluidized bed FBD process of Snamprogetti-Yarsintez company, a steam activated reforming STAR process of Krupp-Uhde, and a PDH process of Linde-BASF company. At present, the industrialized production process for preparing propylene by propane dehydrogenation mainly adopts an Oleflex process of U.S. UOP company, a Pt catalyst and a Catofin process of U.S. CB & I Lummus company, and a Cr-series catalyst. Many units in China are also actively developing relevant catalysts and processes.
The propane dehydrogenation catalytic reaction is carried out at a high temperature of more than 500 ℃ due to thermodynamic limitation of the catalytic reaction, the catalyst is deactivated by carbon deposition along with the reaction, and the development of the catalyst with high activity, high selectivity and high stability becomes the key of the technology. Guo Xia Zhi et al prepared a Ca or Ce modified PtSn/MCM-41 catalyst in the ' influence of Ca or Ce on the structure of the PtSn/MCM-41 catalyst and the performance of catalyzing propane dehydrogenation ' published in ion exchange and adsorption 2013,29(1) ' 16-22, characterized and evaluated the performance of the prepared catalyst in catalyzing propane dehydrogenation, and analyzed the carbon deposition condition of the catalyst after reaction. The results show that the addition of Ca or Ce promoter to the PtSn/MCM-41 catalyst enhances the catalytic performance of propane dehydrogenation, which is not only related to the strong interaction between the promoter and the active component, but also reduces the deactivation of the catalyst caused by carbon deposition.
Propane dehydrogenation catalysts have made greater progress at present, but there is room for improvement in catalyst stability.
Disclosure of Invention
The invention aims to overcome the problem of unstable catalyst performance in the prior art and provide a catalyst which has obviously higher dehydrogenation stability.
The inventor of the invention discovers through research that when the composite oxide carrier contains IIB element and VIII element, the initial temperature of Sn component in the prepared dehydrogenation catalyst beginning to be reduced to Sn is higher than 650 ℃, and the added alkaline earth metal and rare earth metal can generate synergistic effect with the Sn element and the composite oxide carrier, thereby improving the dispersity of Pt element and further improving the stability of the catalyst.
In addition to this, the inventors have found that, when the active component of the catalyst is impregnated onto the composite oxide support, the effect of ultrasonic impregnation is better compared to agitation impregnation, wherein with variable frequency ultrasonic impregnation, the stability and activity of the catalyst are further improved. The reason for this is probably because when the active component of the catalyst is impregnated at a single frequency, some micropores may be clogged with the active component. When the ultrasonic treatment is carried out again at a higher frequency, the blocking state of the micropores can be broken, so that the active components can be diffused into deeper pore channels, the distribution of the active components is more uniform, the combination with the carrier is firmer, and the activity and the stability of the catalyst are further improved.
On the basis of the above-mentioned studies, the first aspect of the present invention provides a catalyst comprising the following components: a) 0.1-5 parts by weight of Pt element; b)0.1 to 5 parts by weight of Sn element; c)0.1 to 2 parts by weight of an alkaline earth metal element; d) 0.1-2 parts by weight of rare earth elements; e) 90-99 parts by weight of a composite oxide A-B-Al-O carrier;
in the composite oxide A-B-Al-O carrier, A is selected from at least one of IIB elements, B is selected from at least one of VIII elements, and Al and A are 1-1.99: 1, Al and B are 1-199: 1.
in a second aspect, the present invention provides a method for preparing a catalyst, comprising the steps of:
a) aging a solution containing A, B and soluble salts of Al elements under the condition that the pH value is 7-9, and then roasting for the first time; wherein A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements; in terms of element molar ratio, Al: A is 1-1.99: 1, Al and B are 1-199: 1;
b) loading soluble salt of Sn onto the roasted product obtained in the step a) by adopting an impregnation method, and then roasting for the second time to obtain a catalyst precursor I;
c) pt, rare earth elements and alkaline earth elements are loaded on the catalyst precursor I, and then the third roasting is carried out.
In a third aspect, the invention provides a use of the catalyst according to the first aspect of the invention or the catalyst obtained by the preparation method according to the second aspect of the invention in the preparation of an olefin by dehydrogenation of an alkane.
In a fourth aspect of the present invention, there is provided a method for preparing an olefin by dehydrogenating an alkane, the method comprising contacting the alkane with steam under the condition of preparing the olefin by dehydrogenating the alkane and in the presence of a catalyst, wherein the catalyst is the catalyst according to the first aspect of the present invention or the catalyst obtained by the preparation method according to the second aspect of the present invention.
The invention adopts A-B-Al-O composite oxide containing IIB element and VIII element as carrier, and adds alkaline earth metal and rare earth element, thereby improving the dehydrogenation stability of the catalyst. In the preparation process, the variable frequency ultrasonic treatment is introduced, so that the stability and the dispersity of the active component on the carrier are further enhanced, and the dehydrogenation stability of the catalyst is further improved. For example, when the catalyst of the invention is used for dehydrogenating propane to prepare propylene, the initial conversion rate of propane is up to 43%, the selectivity of propylene is up to 96%, and the reduction rate of the conversion rate of propane after continuous reaction for 10 hours is not more than 16%. The catalyst has good regeneration performance, and the performance of the catalyst is almost unchanged after 50 times of regeneration tests.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a catalyst comprising the following components: a) 0.1-5 parts by weight of Pt element; b)0.1 to 5 parts by weight of Sn element; c)0.1 to 2 parts by weight of an alkaline earth metal element; d) 0.1-2 parts by weight of rare earth elements; e) 90-99 parts by weight of a composite oxide A-B-Al-O carrier;
in the composite oxide A-B-Al-O carrier, A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements; in terms of element molar ratio, Al: A is 1-1.99: 1, Al and B are 1-199: 1.
in the invention, the composite oxide A-B-Al-O is selected as a carrier, wherein A is selected from at least one of IIB elements, B is selected from at least one of VIII elements, and alkaline earth metal and rare earth elements are added simultaneously, so that the dehydrogenation stability of the catalyst is improved.
Preferably, the catalyst contains the following components: a) 0.1-1.5 parts by weight of Pt element; b)0.1 to 1.5 parts by weight of Sn element; c)0.1 to 1 part by weight of an alkaline earth metal element; d) 0.1-1 part by weight of rare earth elements; e) 92-98 parts by weight of a composite oxide A-B-Al-O carrier.
In the present invention, the above elements are present in the form of oxides, but for convenience of expression, the components other than the A-B-Al-O carrier are all expressed in terms of the content of the elements. Wherein the weight parts of the composite oxide A-B-Al-O carrier are calculated by the mass of the carrier.
The content of all metal elements in the catalyst of the present invention can be measured by using ICP-AES model Varian 710-ES manufactured by Agilent Technologies, USA. Before testing, the solid catalyst powder is dissolved by aqua regia, and then the liquid after dilution and volume fixing is sent to be detected, and finally the content of the metal element in the catalyst is obtained.
In a preferred embodiment, the alkaline earth metal element is selected from at least one of Mg, Ca, Sr, and more preferably Ca.
In a preferred embodiment, the rare earth element is at least one selected from La, Ce, and Y, and more preferably Ce.
In a preferred embodiment, a in the composite oxide a-B-Al-O support is selected from at least one of Zn and Cd, and is more preferably Zn, and B is a metal element other than Pt element in the group VIII element, and may be selected from at least one of Fe, Co, Ni, Ru, Rh, Os, and Ir, and is more preferably at least one of Fe and Co, for example, Fe.
In the composite oxide A-B-Al-O carrier, the molar ratio of Al to A is (1.5-1.9): 1; b is 3-19: 1.
in a preferred embodiment, the catalyst has an initial temperature Ts of 650 to 700 ℃, more preferably 650 to 660 ℃ at which the Sn component begins to be reduced to Sn as measured by a hydrogen temperature programmed method.
Among the catalysts for producing olefins by dehydrogenation of alkanes, the catalyst for producing propylene by dehydrogenation of propane is exemplified, and the Sn reduction temperature is about 600 ℃. However, in the catalyst of the invention, the Sn reduction temperature is higher than 650 ℃, and the high Sn reduction temperature shows that the element has strong action with the carrier, so that the performance of the catalyst is more stable.
In the present invention, the hydrogen programmed heating method is H2TPR test method. H2The TPR test is carried out on an AutoChem 2920 dynamic adsorption apparatus, Michkogaku corporation, and the specific test conditions are as follows: with H2The hydrogen-argon mixed gas with the volume fraction of 10 percent is reducing gas, the sample dosage is 50mg, the gas flow rate is 50mL/min, the sample temperature is increased from room temperature to 750 ℃, and the temperature rising rate is 10 ℃/min.
In a preferred embodiment, the conversion rate of the catalyst to propane is 43 to 45%, and more preferably 43.5 to 44.5%; after 10 hours of continuous reaction, the reduction rate of the conversion rate of propane is not more than 16%, and more preferably not more than 11%.
In a second aspect, the present invention provides a method for preparing a catalyst, comprising the steps of:
a) aging a solution containing A, B and soluble salts of Al elements under the condition that the pH value is 7-9, and then roasting for the first time, wherein A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements; in terms of element molar ratio, Al: A is 1-1.99: 1, Al and B are 1-199: 1;
b) loading soluble salt of Sn onto the roasted product obtained in the step a) by adopting an impregnation method, and then roasting for the second time to obtain a catalyst precursor I;
c) pt, rare earth elements and alkaline earth elements are loaded on the catalyst precursor I, and then the third roasting is carried out.
In the step a) of the process,
in a preferred embodiment, a is selected from at least one of Zn and Cd, further preferably Zn; b is preferably at least one of Fe, Co, Ni, Ru, Rh, Os, and Ir, and more preferably at least one of Fe and Co, for example, Fe.
The soluble salt of A, B and Al is not particularly limited in the present invention, and preferably, the soluble salt of A, B and Al may be at least one selected from chloride, sulfate, nitrate and acetate, and preferably is nitrate.
In a preferred embodiment, Al: A is 1.5 to 1.9 in terms of molar ratio of elements: 1; b is 3-19: 1.
in a preferred embodiment, A, B and the soluble salt of Al are mixed well in deionized water. Wherein the addition amount of the deionized water is 0.8-2L, preferably 1-1.5L based on the total mass of 1000g of A, B and Al soluble salt.
In a preferred embodiment, the environment with the pH value of 7-9 is obtained by adding a base, wherein the base is at least one selected from ammonia water, triethylamine, dimethylamine, aniline and pyridine, more preferably at least one selected from ammonia water, triethylamine and dimethylamine, and even more preferably ammonia water.
In a preferred embodiment, the alkali is added dropwise under stirring, and the pH of the solution is adjusted to 7 to 9, preferably 7.5 to 8.5 by slowly adding the alkali dropwise. Wherein, by controlling the dropping speed of the alkali, the phenomenon that the pH value of the solution is changed too much instantly to influence the performance of the finally obtained catalyst can be prevented.
In a preferred embodiment, the aging is carried out at room temperature for 1 to 4 hours, preferably 2 to 2.5 hours. The room temperature is not particularly limited, and can be 20-40 ℃, and preferably 25-35 ℃.
Wherein, the aging in the invention is the process of standing the material in the environment.
In a preferred embodiment, the first roasting is performed at 550 to 650 ℃ for 6 to 24 hours, and preferably at 600 to 650 ℃ for 18 to 20 hours.
In a preferred embodiment, the separation operation is performed after aging. In the present invention, the separation method is not particularly limited, and suction filtration is preferable.
In order to obtain better roasting effect, it is preferable that the separated product is subjected to a first drying treatment before the first roasting. The first drying temperature is 80-150 ℃, the first drying time is 6-24 hours, and the first drying time is 16-20 hours.
In the step b) of the process,
in a preferred embodiment, the soluble salt of Sn is used in an amount of 0.1 to 5 parts by weight in terms of Sn element, relative to 90 to 99 parts by weight of the calcined product obtained in step a); further preferably, the soluble salt of Sn is used in an amount of 0.1 to 1.5 parts by weight in terms of Sn element, relative to 92 to 98 parts by weight of the calcined product obtained in step a).
Wherein, the soluble salt of Sn can be at least one selected from stannous chloride and stannic chloride, and the weight parts of the roasting product obtained in the step a), namely the composite oxide A-B-Al-O carrier, are calculated by the weight of the roasting product.
In a preferred embodiment, the calcined product of step a) is mixed homogeneously with a soluble salt of Sn in an acid solution.
Wherein the acid solution is preferably hydrochloric acid, and the concentration of the hydrochloric acid is 0.1-2 mol/L, preferably 0.5-1.5 mol/L; the amount of the acid solution added is 5 to 20ml, preferably 10 to 12ml, based on 10g of the calcined product in the step a).
In a preferred embodiment, the impregnation in step b) comprises first contacting in the presence of ultrasound and then leaving the contacting still; preferably, the contacting in the presence of ultrasonic waves comprises firstly performing ultrasonic treatment for 1-4 hours at 10-25 kHz, and then performing ultrasonic treatment for 2-6 hours at 30-50 kHz; the standing and contacting conditions comprise that the temperature is 10-80 ℃, the preferable temperature is 30-50 ℃, and the time is 1-24 hours, and the preferable time is 12-16 hours.
In a preferred embodiment, the second roasting temperature is 550-650 ℃, preferably 600-650 ℃, and the second roasting time is 6-24 hours, preferably 18-20 hours.
In the present invention, the selection of the ultrasonic frequency is not particularly limited, and may be selected depending on the amount of the impregnation solution to be treated. Wherein, the dispersion of the impregnated tin ions on the surface of the carrier is further enhanced by proper frequency conversion ultrasound in the step b), and the sufficient interaction of the Sn component and the carrier in the roasting process is ensured, so that the stability of the Sn component is enhanced, and the dehydrogenation stability of the catalyst is improved.
In order to obtain better roasting effect, it is preferable to subject the product obtained after impregnation in step b) to a second drying treatment before the second roasting. The second drying temperature is 80-150 ℃, preferably 100-120 ℃, and the second drying time is 6-24 hours, preferably 16-20 hours.
In the step c) of the process,
in a preferred embodiment, relative to 90 to 99 parts by weight of the roasted product obtained in the step a), the supported amount of the soluble salts of Pt, the rare earth elements and the alkaline earth elements is 0.1 to 5 parts by weight of Pt, and the supported amount of the soluble salts of Pt, the rare earth elements and the alkaline earth elements is 0.1 to 2 parts by weight of each;
more preferably, the supported amount of the soluble salts of Pt, the rare earth elements and the alkaline earth elements is 0.1 to 1.5 parts by weight of Pt, and the supported amount of the soluble salts of Pt, the rare earth elements and the alkaline earth elements is 0.1 to 1 part by weight of the rare earth elements and the alkaline earth elements respectively, relative to 92 to 98 parts by weight of the roasted product obtained in the step a).
The soluble salt of Pt is preferably chloroplatinic acid, and the soluble salt of rare earth elements and alkaline earth metals can be one of chloride, sulfate, nitrate or acetate, and is preferably nitrate.
In a preferred embodiment, soluble salts of Pt, rare earth elements, and alkaline earth elements are dissolved in water, and Pt, rare earth elements, and alkaline earth elements are supported on the catalyst precursor I by impregnation.
In a preferred embodiment, the pH value of the dipping solution is adjusted to 1-3, preferably 1.5-2.5 by adding acid.
Wherein the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, preferably from at least one of hydrochloric acid, sulfuric acid and nitric acid, and more preferably hydrochloric acid.
In a preferred embodiment, the loading in step c) comprises firstly carrying out ultrasonic treatment at 10-25 kHz for 1-4 h, then carrying out ultrasonic treatment at 30-50 kHz for 2-6 h, and then carrying out standing contact.
In a preferred embodiment, the conditions of the standing contact in the step c) include a temperature of 10 to 80 ℃, preferably 30 to 50 ℃, and a time of 1 to 24 hours, preferably 12 to 16 hours.
Wherein, the pH value of the impregnation liquid is adjusted in the step c) and the frequency conversion ultrasonic treatment is carried out in the step b) and the step c), which is beneficial to chloroplatinic acid radical [ PtCl ]6]2-And lanthanide elements and alkaline earth metal ions are dispersed, so that the lanthanide elements and the alkaline earth metal ions have sufficient action with Pt and Sn components, and are dispersed more uniformly, thereby improving the reduction temperature of Sn and being beneficial to the dehydrogenation stability of the catalyst.
In the present invention, the impregnation in step b) and step c) may be saturated impregnation or equivalent-volume impregnation as long as the desired component is supported on the carrier.
In a preferred embodiment, the third roasting temperature is 550-650 ℃, preferably 600-650 ℃, and the third roasting time is 6-24 hours, preferably 18-20 hours.
In order to obtain better roasting effect, it is preferable that the product obtained after impregnation in step c) is subjected to a third drying treatment before the third roasting. The third drying temperature is 80-150 ℃, the preferable drying temperature is 100-120 ℃, and the third drying time is 6-24 hours, and the preferable drying time is 16-20 hours.
In the present invention, the conditions for the three times of calcination may be the same or different. The conditions for the third drying may be the same or different.
In a third aspect, the invention provides a use of the catalyst according to the first aspect of the invention or the catalyst obtained by the preparation method according to the second aspect of the invention in the preparation of an olefin by dehydrogenation of an alkane.
In a fourth aspect of the present invention, there is provided a method for preparing an olefin by dehydrogenating an alkane, the method comprising contacting the alkane with steam under the condition of preparing the olefin by dehydrogenating the alkane and in the presence of a catalyst, wherein the catalyst is the catalyst according to the first aspect of the present invention or the catalyst obtained by the preparation method according to the second aspect of the present invention.
In a preferred embodiment, the alkane is selected from the group consisting of C2 to C6 alkanes, more preferably C3 to C4 alkanes, and even more preferably propane.
At one isIn a preferred embodiment, the reaction conditions are: the volume ratio of the water vapor to the alkane is (1-10) to 1, preferably (2-6): 1; the reaction temperature is 400-600 ℃, and preferably 500-550 ℃; the reaction pressure (gauge pressure) is 0 to 1MPa, preferably 0.5 to 1 MPa; the mass space velocity of the alkane is 3-8 h-1, preferably 5 to 6 hours-1(ii) a The reaction time is 6-20 h, preferably 10-12 h.
Unless otherwise specified, the reaction pressure in the present invention is a gauge pressure.
The following examples are given to illustrate the technical aspects of the present invention in detail, but the present invention is not limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention, based on the common technical knowledge in the field and the similar means.
Wherein, in the examples and comparative examples,
H2the TPR test was carried out on an AutoChem 2920 dynamic adsorption apparatus from Michk instruments USA, using a H2The hydrogen-argon mixed gas with the volume fraction of 10 percent is reducing gas, the sample dosage is 50mg, the gas flow rate is 50mL/min, the sample temperature is increased from room temperature to 750 ℃, and the temperature rising rate is 10 ℃/min.
In the prepared carrier and the catalyst, the weight parts of the components are measured by an ICP-AES measuring method. Before testing, the solid catalyst powder is dissolved by aqua regia, and then the liquid after dilution and volume fixing is sent to be detected, and finally the content of the metal element in the catalyst is obtained.
In the present invention, the stability of the catalyst refers to a decrease rate of the conversion rate of the alkane after a continuous reaction for a certain period of time. The less the decrease in alkane conversion with longer reaction times, the better the catalyst stability.
In the present invention, the regeneration performance of the catalyst refers to the catalytic activity and stability of the catalyst after reaction is regenerated by a carbon burning treatment.
Wherein, the reduction rate of the alkane conversion rate is calculated in the following way: the ratio of the amount of decrease in alkane conversion after a period of reaction time to the initial alkane conversion.
Example 1
1) Preparation of the catalyst
a) 297.49g of zinc nitrate, 121.23g of ferric nitrate nonahydrate and 637.72g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 7.8, the product is aged for 2h at room temperature, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 16h at 100 ℃, and is roasted for 20h in a 600 ℃ muffle furnace to obtain a composite oxide carrier, which is marked as C-1, the element content of the composite oxide carrier is tested, and the result is shown in Table 1.
b) 9.73g of the carrier was weighed into a beaker, and then 0.190g of stannous chloride dihydrate was weighed and dissolved in 10mL of hydrochloric acid (concentration: 1mol/L) and mixed with stirring, followed by ultrasonic mixing at 20 kHz for 2h and ultrasonic mixing at 40 kHz for 4h, and dipping at 30 ℃ for 12 h. Then drying the catalyst for 16h at 100 ℃, and roasting the catalyst for 20h in a muffle furnace at 600 ℃ to obtain the catalyst precursor.
c) Weighing 0.106g of chloroplatinic acid, 0.472g of calcium nitrate and 0.116g of anhydrous cerium nitrate, dissolving in 10mL of water, adding hydrochloric acid to adjust the pH value to 2.5, mixing with the catalyst precursor obtained in the step b) while stirring, then carrying out ultrasonic treatment at 20 kilohertz for 2 hours, carrying out ultrasonic treatment at 40 kilohertz for 4 hours, uniformly mixing, dipping at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, roasting at 600 ℃ in a muffle furnace for 20 hours to obtain the propane dehydrogenation catalyst, and testing the element content of the catalyst, wherein the results are shown in Table 2.
2) Characterization of the catalyst
Subjecting the above catalyst to H2TPR test, the results of which are shown in FIG. 1 and Table 2.
3) Evaluation of catalyst
The catalyst was evaluated using an isothermal fixed bed reactor under the following conditions: the reactor is a stainless steel sleeve with the inner diameter of phi 9 mm-phi 6mm and the length of 400 mm. 0.5 g of catalyst is loaded into the isothermal fixed bed reactor (the height of a catalyst bed layer is 17mm), the reaction pressure is normal pressure, and the temperature is 550 ℃; the volume ratio of the water vapor to the propane is 2: 1; the mass space velocity of the propane is 5h-1The reaction was continued for 10h, and the results are shown in Table 3.
Wherein, the initial propane conversion rate refers to the instantaneous conversion rate after 5min of reaction, and the 10h propane conversion rate refers to the instantaneous conversion rate after 10h of continuous reaction. The initial propylene selectivity refers to the instantaneous selectivity after 5min of reaction, and the 10h propylene selectivity refers to the instantaneous selectivity after 10h of continuous reaction.
Example 2
1) Preparation of the catalyst
a) 297.49g of zinc nitrate, 121.23g of ferric nitrate nonahydrate and 637.72g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to be 8.0, the product is aged for 2.5h at room temperature, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 16h at 120 ℃, and then is roasted for 20h in a 600 ℃ muffle furnace to obtain a composite oxide carrier, which is marked as C-1-1, and the element content of the composite oxide carrier is tested, and the result is shown in Table 1.
b) Weighing 9.73g of carrier and placing the carrier into a beaker, then weighing 0.190g of stannous chloride dihydrate and dissolving the stannous chloride dihydrate in 10mL of hydrochloric acid (the concentration is 0.5mol/L), mixing the mixture while stirring, then carrying out ultrasonic treatment for 4h at 10 KHz, carrying out ultrasonic treatment for 6h at 30 KHz, uniformly mixing the mixture, dipping the mixture for 16h at 50 ℃, then drying the mixture for 20h at 100 ℃, and roasting the dried mixture for 19h in a muffle furnace at 625 ℃ to obtain the catalyst precursor.
c) Weighing 0.106g of chloroplatinic acid, 0.472g of calcium nitrate and 0.116g of anhydrous cerium nitrate, dissolving in 10mL of water, adding hydrochloric acid to adjust the pH value to 1.5, mixing with the catalyst precursor obtained in the step b) while stirring, then carrying out ultrasonic treatment at 25 kilohertz for 1h, carrying out ultrasonic treatment at 50 kilohertz for 2h, uniformly mixing, soaking at 30 ℃ for 16h, drying at 120 ℃ for 16h, roasting at 650 ℃ in a muffle furnace for 18h to obtain the propane dehydrogenation catalyst, and testing the element content of the catalyst, wherein the results are shown in Table 2.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 3
1) Preparation of the catalyst
a) 297.49g of zinc nitrate, 121.23g of ferric nitrate nonahydrate and 637.72g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.5, the product is aged for 2h at room temperature, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 20h at 100 ℃, and then is roasted for 18h in a muffle furnace at 650 ℃, so that a composite oxide carrier is obtained, which is marked as C-1-2, and the element content of the composite oxide carrier is tested, and the result is shown in Table 1.
b) Weighing 9.73g of carrier and placing the carrier into a beaker, then weighing 0.190g of stannous chloride dihydrate and dissolving the stannous chloride dihydrate in 10mL of hydrochloric acid (the concentration is 1.5mol/L), mixing the mixture while stirring, then carrying out ultrasonic treatment for 1h at 25KHz, carrying out ultrasonic treatment for 2h at 50KHz, uniformly mixing the mixture, dipping the mixture for 14h at 40 ℃, then drying the mixture for 18h at 110 ℃, and roasting the dried mixture for 20h in a 600 ℃ muffle furnace to obtain the catalyst precursor.
c) Weighing 0.106g of chloroplatinic acid, 0.472g of calcium nitrate and 0.116g of anhydrous cerium nitrate, dissolving in 10mL of water, adding hydrochloric acid to adjust the pH value to 2, mixing with the catalyst precursor obtained in the step b) while stirring, then carrying out ultrasonic treatment at 10 KHz for 4h, carrying out ultrasonic treatment at 30 KHz for 6h, uniformly mixing, dipping at 50 ℃ for 12h, drying at 120 ℃ for 16h, roasting at 650 ℃ in a muffle furnace for 18h to obtain the propane dehydrogenation catalyst, and testing the element content, wherein the results are shown in Table 2.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 4
A catalyst was prepared according to the method of example 1 except that in step a) Al: Zn ═ 1.5 and Al: Fe ═ 3, and the prepared support was designated C-2.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 5
A catalyst was prepared according to the procedure of example 1 except that in step a) Al: Zn ═ 1.9 and Al: Fe ═ 19, and the prepared support was designated C-3.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 6
A catalyst was prepared as in example 1, except that:
changing the using amount of stannous chloride dihydrate in the step b) and the using amount of chloroplatinic acid, calcium nitrate and anhydrous cerium nitrate in the step C) to make the adding amount of Sn element be 2.5 parts by weight, the adding amount of Pt element be 2.5 parts by weight, the adding amount of Ca element be 1 part by weight and the adding amount of Ce element be 1 part by weight based on 93 parts by weight of the composite oxide carrier C-1.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 7
A catalyst was prepared by the method of example 1, except that,
changing the using amount of stannous chloride dihydrate in the step b) and the using amount of chloroplatinic acid, calcium nitrate and anhydrous cerium nitrate in the step C) to ensure that the adding amount of Sn element is 0.8 part by weight, the adding amount of Pt element is 0.8 part by weight, the adding amount of Ca element is 0.5 part by weight and the adding amount of Ce element is 0.5 part by weight based on 97.4 parts by weight of the composite oxide carrier C-1.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 8
A catalyst was prepared by the method of example 1, except that,
changing the using amount of stannous chloride dihydrate in the step b) and the using amount of chloroplatinic acid, calcium nitrate and anhydrous cerium nitrate in the step c) so that the adding amount of Sn element is 1.5 parts by weight, the adding amount of Pt element is 1.5 parts by weight, the adding amount of Ca element is 1 part by weight and the adding amount of Ce element is 1 part by weight based on 95 parts by weight of the composite oxide carrier.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 9
1) Preparation of the catalyst
The catalyst was prepared according to the method of example 1, except that in step c) the pH was adjusted to 2.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 10
1) Preparation of the catalyst
The catalyst was prepared according to the method of example 1, except that in step c) the pH was adjusted to 1.5.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 11
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
in step b) the mixture was mixed homogeneously by sonication for 6h only at 20 kHz.
In step c) the mixture was mixed homogeneously by sonication for 6h only at 20 kHz.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Example 12
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
in step b) the mixture was mixed homogeneously by sonication for 6h only at 40 kHz.
In step c) the mixture was mixed homogeneously by sonication for 6h only at 40 kHz.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 1
1) Preparation of the catalyst
297.49g of zinc nitrate and 750.26g of soluble aluminum nitrate nonahydrate salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in the mixture under continuous stirring, the pH value is adjusted to be 7.8, the product is aged for 2h, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried at 100 ℃ for 16h and then roasted in a 600 ℃ muffle furnace for 20h to obtain a carrier, the carrier is marked as D-1, and the element content of the carrier is tested, and the result is shown in Table 1.
Weighing 9.86g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid (with the concentration of 1mol/L), uniformly mixing the mixture while stirring, soaking the mixture for 12 hours at the temperature of 30 ℃, then drying the mixture for 16 hours at the temperature of 100 ℃, and roasting the dried mixture for 20 hours in a muffle furnace at the temperature of 600 ℃ to obtain the catalyst precursor.
Weighing 0.106g of chloroplatinic acid, dissolving in 10mL of water, adjusting the pH value to 2.5 by using hydrochloric acid, adding the catalyst precursor under stirring, uniformly mixing, dipping for 12h at 30 ℃, drying for 16h at 100 ℃, and roasting for 20h in a 600 ℃ muffle furnace to obtain the propane dehydrogenation catalyst, wherein the element content is tested, and the results are shown in Table 2.
2) Characterization of the catalyst
The catalyst characterization procedure was the same as in example 1, and the results are shown in FIG. 1 and Table 3.
From the test results, it is understood that the reduction temperature Ts of the Sn component of the catalyst of example 1 is 663 deg.C, and the reduction temperature Ts of the Sn component of comparative example 1 is 550 deg.C. The reduction temperature of the Sn component in example 1 is significantly higher than that in comparative example 1, indicating that the Sn and the support act more strongly and the catalyst is more stable in example 1.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 2
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
in step a) copper nitrate was used instead of zinc nitrate, where Al: Cu ═ 1.7, and the catalyst support prepared was designated D-2.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 3
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
manganese nitrate was used in place of ferric nitrate in step a), where Al: Mn ═ 5.67, and the catalyst support prepared was designated D-3.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 4
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
in step a) the zinc nitrate was replaced by copper nitrate and the iron nitrate was replaced by manganese nitrate, with Al: Cu 1.7 and Al: Mn 5.67, and the catalyst support prepared was designated D-4.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 5
1) Preparation of the catalyst
A catalyst was prepared as in example 1, except that:
in step c) 0.472g of calcium nitrate and 0.116g of anhydrous cerium nitrate were not added.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 6
1) Preparation of the catalyst
The catalyst was prepared according to example 2 in CN 109651048A.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 7
1) Preparation of the catalyst
The catalyst was prepared according to example 2 in CN 109647391A.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
Comparative example 8
1) Preparation of the catalyst
The catalyst was prepared according to example 2 in CN 109651047A.
2) Characterization of the catalyst
The catalyst was characterized as in example 1 and the results are shown in Table 3.
3) Evaluation of catalyst
The catalyst evaluation method was the same as in example 1, and the results are shown in Table 3.
TABLE 1
Figure BDA0002555780470000201
TABLE 2
Figure BDA0002555780470000211
TABLE 3
Figure BDA0002555780470000221
As can be seen from the results in Table 3, when the catalyst of the present invention is used for dehydrogenation of propane to produce propylene, the conversion rate of propylene is as high as 43%, the selectivity of propylene is as high as 96%, after 10 hours of continuous reaction, the conversion rate of propane is not more than 16%, and the stability of the catalyst is obviously improved.
Test example 1
The catalysts reacted in example 1, example 11, comparative example 4 and comparative example 6 were calcined at 550 ℃ for 2 hours under an air atmosphere to obtain regenerated catalysts, and then the evaluation was repeated according to the catalyst evaluation method in example 1. Evaluation-regeneration the operation was repeated 50 times, during which the test was stopped when the conversion of the catalyst was less than 38%. The specific test results are shown in table 4.
TABLE 4
Figure BDA0002555780470000231
As can be seen from the results in Table 4, the catalyst of the present invention has good regeneration performance, and the conversion rate is substantially maintained after 50 cycles of the test.

Claims (12)

1. A catalyst comprising the following components: a) 0.1-5 parts by weight of Pt element; b)0.1 to 5 parts by weight of Sn element; c)0.1 to 2 parts by weight of an alkaline earth metal element; d) 0.1-2 parts by weight of rare earth elements; e) 90-99 parts by weight of a composite oxide A-B-Al-O carrier;
in the composite oxide A-B-Al-O carrier, A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements; in terms of element molar ratio, Al: A is 1-1.99: 1, Al and B are 1-199: 1.
2. the catalyst of claim 1, wherein the catalyst comprises the following components: a) 0.1-1.5 parts by weight of Pt element; b)0.1 to 1.5 parts by weight of Sn element; c)0.1 to 1 part by weight of an alkaline earth metal element; d) 0.1-1 part by weight of rare earth elements; e) 92-98 parts by weight of a composite oxide A-B-Al-O carrier.
3. The catalyst according to claim 1 or 2, wherein the alkaline earth metal element is selected from at least one of Mg, Ca, Sr, and the rare earth element is selected from at least one of La, Ce, Y.
4. The catalyst according to any one of claims 1 to 3, wherein in the composite oxide A-B-Al-O support, A is selected from at least one of Zn and Cd, and B is selected from at least one of Fe and Co.
5. The catalyst according to any one of claims 1 to 4, wherein the catalyst has an initial temperature Ts of 650 to 700 ℃ at which the Sn component begins to be reduced to Sn as measured by a hydrogen temperature programmed method.
6. A method of preparing a catalyst comprising the steps of:
a) aging a solution containing A, B and soluble salts of Al elements under the condition that the pH value is 7-9, and then roasting for the first time; wherein A is selected from at least one of IIB elements, and B is selected from at least one of VIII elements; in terms of element molar ratio, Al: A is 1-1.99: 1, Al and B are 1-199: 1;
b) loading soluble salt of Sn onto the roasted product obtained in the step a) by adopting an impregnation method, and then roasting for the second time to obtain a catalyst precursor I;
c) pt, rare earth elements and alkaline earth elements are loaded on the catalyst precursor I, and then the third roasting is carried out.
7. The process according to claim 6, wherein in step a), the aging conditions comprise a temperature of room temperature, preferably 20 to 40 ℃, for 1 to 4 hours.
8. The process according to claim 6 or 7, wherein, in step b), the impregnation comprises first contacting in the presence of ultrasound and then still contacting; preferably, the contacting in the presence of ultrasonic waves comprises firstly performing ultrasonic treatment for 1-4 hours at 10-25 kHz, and then performing ultrasonic treatment for 2-6 hours at 30-50 kHz;
preferably, the soluble salt of Sn is used in an amount of 0.1 to 5 parts by weight in terms of Sn element, relative to 90 to 99 parts by weight of the calcined product obtained in step a).
9. The method according to any one of claims 6 to 8, wherein in step c), the loading comprises firstly performing ultrasound at 10 to 25kHz for 1 to 4 hours, then performing ultrasound at 30 to 50kHz for 2 to 6 hours, and then standing;
preferably, relative to 90-99 parts by weight of the roasted product obtained in the step a), the supported amounts of Pt, the rare earth element and the alkaline earth element are 0.1-5 parts by weight of Pt and 0.1-2 parts by weight of each of the rare earth element and the alkaline earth element.
10. Use of the catalyst according to any one of claims 1 to 5 or the catalyst obtained by the preparation method according to any one of claims 6 to 9 for the dehydrogenation of alkanes to olefins.
11. A method for preparing olefin by dehydrogenating alkane, which comprises contacting alkane with steam under the condition of preparing olefin by dehydrogenating alkane and in the presence of a catalyst, and is characterized in that the catalyst is the catalyst as claimed in any one of claims 1 to 5 or the catalyst obtained by the preparation method as claimed in any one of claims 6 to 9.
12. The method of claim 11, wherein the conditions for dehydrogenating the alkane to produce the alkene comprise a temperature of 400 ℃ to 600 ℃, preferably 500 ℃ to 550 ℃; the pressure is 0-1 MPa, preferably 0.5-1 MPa; the mass space velocity of the alkane is 3-8 h-1Preferably 5 to 6 hours-1(ii) a The volume ratio of the water vapor to the alkane is (1-10) to 1, preferably (2-6): 1.
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